Textile printing pastes and method of applying



United States Patent TEXTILE PRINTING PASTES OF APPLYING AND METHOD No Drawing. Application May 27, 1953,

Serial No'. 357,922

. Claims priority, application Germany August 3, 1949 10 Claims. (Cl. 117-63) The present invention relates to improvements in the printing and dyeing of textiles of any kind with pigment dyestulfs and more particularly to a novel printing paste.

This application is a continuation in part of our copending application Ser. No. 117,262, filed September 22, 1949, now Patent No. 2,643,958.

According to the hitherto known processes for printing and dyeing textiles with pigments, for the most part ready made film-forming compositions are used as binders. These binders have to be water insoluble in order to ensure a fixation of the pigments that is fast to Washing. Therefore, the film-forming agents must be employed in the printing or padding pastes either in the form of asolution in organic solvents or in the form of an aqueous suspension or emulsion in a mixed aqueous-organicv medium. The additional use of organic solvents causes many inconveniences in print and dye works. On the other hand, printing or ing agents in the form of pure aqueous only insufficiently stable and, furthermore, advantage that the binder does not emulsions are havethe dismediately on contacting the fabric, the erties being impaired-thereby.

It has also been proposed to produce the film-forming agent on the fiber, viz. from components which are added to the printing pastes or padding solutions in a water-- soluble condition, for instance, from phenol and'formaldehyde. Films, thus obtained, however, possess poor mechanical properties. In particular they are too brittle and 'in consequence thereof fastness to rubbing is poor. Furthermore, film-forming compositions of this kind can be obtained only under very severe conditions. Such processes, therefore, have not proved to be useful in practice. V I

It is therefore an object of our invention to provide a binding agent for the pigment or dyestutf soluble in aqueous printing or padding pastes.

A further object resides in the provision of binding agents readily convertible into insoluble, supple and elastic films on the fibrous material.

Another object is to provide a printing paste which will fix the pigment on the fabric fast to washing and which will not impair the feel or hand of the .goods.

A still further object of the invention is to provide a process of decorating textile fabrics.

Still further objects will become apparent as the following specification proceeds.

The objects of the invention are accomplished by using as a printing paste a composition having the following characteristics:

(a) As film-forming compositions, resinous polyamines having recurring basic radicals selected from the group consisting of primary and secondary amino groups, which polymers are water soluble per se their salts with acids,

padding pastes containing film-form or in the form of 1 cross-linking reaction 2,762,718 Patented Sept. 11, 1956 2 Y (b) They are present in printing and padding pastes in form of such salts in aqueous solutions,

(c) The printing and padding pastes, furthermore, contain polyfunctional compounds capable of reacting with amino or imino groups (hereinafter called crosslinking agents) which at normal temperatures are at least difiicultly soluble in water and are finely distributed in the printing or padding pastes.

Printing or padding pastes prepared according to the dyestuffs the usual additions, such as thickening agents, glycerine etc., are stable at ordinary temperature for some days, or even .for some weeks, which renders them suitable for, practical application in print and dye works. Their stability isv due to the fact that the reactivity of the polymers containing aminoor imino' groups is checked by salt formation with the acids. The stability of such printing or padding pastes, however, can be 'over padded'material, for instance, can be subjected to an alkaline aftertreatment. By this treatment the film-forming compositions on the fiber are set free from their salts in an insoluble state, and by liberating the basic groups the conditions are provided for the additional with the compounds described (sub 0).

Another processing method of our invention consists in--employing the resinous polyamines in form of their water-soluble salts withvolatile acids. In this case, precipitation of the film-forming composition upon the fiber and subsequent cross-linking can be effected simply by drying, since the volatile acids evaporate and by setting free the basic groups provide the conditions required for cross-linking. 1 Which way is the better depends on the spe cial .conditions of the printing or dyeing process concerned. For instance, preference is given to the alkaline development, if printing is effected in combination'with dyestuffs other than pigments, for instance, vat or' coupling dyes which per se require an alkaline aftertreatment, or if a wet a special finishing effect. and formic acid are preferred.

The process according to the present invention combines the advantages of the known processes referred to above without exhibiting the disadvantages thereof.

The use of organic solvents can be dispensed with and the process can be performed in a purely aqueous medium. The film-forming compositions are soluble in the aqueous printing or padding pastes and, therefore, easily penetrate the fiber. Furthermore, they become insoluble by the alkaline aftertreatment or heating in the presence of cross-linking agents and consequentlyinsure a fixation which is fast to washing, acids and alkalies. Despite the cross-linking the film-forming compositions are distinguished by good elasticity and suppleness, properties characteristic for polyvinyl ester, so that a good fast ness to rubbing is guaranteed and the feel of the fibrous material is not impaired. Fixing'by drying already takes place at moderate temperatures of, for in- I C. within a few minutes. Fixing by an alkaline aftertreatment is also carried out within a few minutes. v

- Such compounds are suitable as binders as contain two or more primary or secondary amino-groups and are just soluble in water per se or in the form of their salts, their solubility being'so adjusted that it can be removed easily and completely by a cross-linking-reaction. It is necessary to produce an insoluble, high molecular weight form on the textile material, which should preferaly also be fixed in the textile material. Reaction components should therefore be used, which are not too operation is necessary for achieving As volatile acids, aceticacid macromolecular, sinc'ecompounds of too high a molecular weight do .not penetrate sufficiently into the textile material.

The effect desired may be obtained with various polyamines and various cross-linking agents. Of the polyamines those "having a comparatively high molecular Weight possess the solubility Characteristics mentioned above; As alower limit a minimum molecular weight of about-200 appears necessary. The maximum molecu: lar weight" is limited by the beginning insolubilization of the 'rnacror'nolecular polyarnine." The molecular weight and reactivity of each p'olya'mine should be, adjusted to"the r'nolecular' weight and reactivity of each cross linking agent. If the polyaminejfor instance has a lownifolecular weight and only a'few reactive groups.

e "crossrli'nking;agent should have a great number. of

reactive "groups. In those, casesfwhe ren the amine has; thecharactferbf. a, macromolecular empowers or less-active reactive groups in theIfcross-linking} agent are;

" "jnft. Polymeric, amines est-amea'aei' en m pr pl d un t "Obviously, "the resinousrpolyamine should-be fre efrom groups other than'the primary or secondary amino groups, which other groups wouldip referentially, react with thfe polyfune'tional' compound, since. such reaction. would j impair are desired cross linking reactionv of the. amiiidgroups,

""Amon'gthe'resinous polyamines suitable asrbinders, according to our inventiori are the, polymeric, esters containing amino-or imino groups, preferably those .de-, rived, fromsacrylic or methacrylic a cid;ester. Naturally further components, such as vinyl esters, styrene or. butadiene, may becopolymerized therewith. Furthermore,

copolyrnersofother esters, for instancefumaric or .maleic acid ,ester, vv'th, the above polymerization components mayjb eremployed The amino,- orimino groups can beintroduced -into thelpolymeric esters in, various ways. Forinstance, acrylicrestermay be subjectedto copolymerization,withacrylonitrile, and the nitrile groups of thepolymer .then totally or partly reduced to amino groups, Another. way consists in;.copolymerizing acrylic ester withacrylamide, adding the copoly-mer obtainedtoanr'acrylonitrile polymer and then reducing thenitrile group. to an amino -group. Other possibilities consist in reacting .polyacrylic-ester and ethanol amine and adding acrylonitrile or cyanoethyl'isocyanate 'orethyle rie imine' with a diamine, for instance methyl-propylene-diamine, in the molecular proportion 1:1.

Furthermore polymers containing groups capable of reduction or hydrogenation, for instance, nitroor nitrile groups may be converted into basic polymers by the action of nascent or catalytically activated hydrogen.

According to PatentNo. 2,122,707 it is possible to render polyvinylmethylketones basic and watersoluble by reaction with ammonia. These basic resins may bemade insoluble by heating, If they are cross-linked with bifunctional compoundsaccording tothe present invention they can be fixed much more quickly: and much more effectively.

Furthermore polyaprylicacid nitrile may be converted into watersoluble derivatives-probably basioamidines by theaction of boilingapolyamines; for instance ethylene diamine.

Polyvinylamines may be obtained by saponification of po meric, vinyl ue pimid n vinyl. p l mi ey iaise gh d eziaeh ra p ef y e net to the hydroxyethyl-amide groupsobtained, arnino gro ups being-fformed either directly or after subsequent reducv tiona Still.Qanotherpossibilty consistsfin first partially saponifyi'ng' 'tlie polyacrylic ester and then causing it] torea'etwith cyano ethyl-isocyanate. In this case a car bonafriide link is formed wit the evolutionfof carbon dioxide, the eyan groiip introduced being later redu ced wan amine group, "Afpa'rticulafrly simple method} rot-f the production of the 'startin'g' materials consists inconvi densing'polymersf containing ester 'groupsl'with bior polyfunctional amines, "such as ethylene 'diamine,, diethylene t'riamine, tetrarnethylene diamine, hexamethylenej'dir aniine, blF-hiethylpropylene diamine, 'N'-isobutylpropylene di'afmine and diairiinesf 'with hetero-atoms or hetero. sq ps'; u s reached where a combined but are 'still soluble 'in aqueous acids or .orgain "solvents ormfusible. This. intermediate stage, can, easilybe maintained; Preferably the components: are heated in -the prcsence of an organic solvent for this-purpose, Basic, groups may be introduced into the polymers. in various ways, for instance by.polymerizing therewith compounds capable ofs reaction with dior polyamines inrsuch a manner that basic. groups remain in the finalprdduct. As'a n example of the many possibilitiesmay be mentioned the int erpolymerization of styrene a ndacryL fluoride/and the subsequentreaction ofthe .interpolymi er diamirio-dipropylether,. astate is; the comp orients. .are i'already chemicallyby reacting a Basic polyesters may be obtained from. isocyanate: modified polyesters as they are for instance-described in theco-pending application Serial.No. 70,598 2filed1121nuary,l2, 1949,- by;-Miil ler; et al., by ireaction-withidior po yam es- Furthermore allthose high molecular weight compounds areisuitedfor. the; process according to-the in vention in which halogenatoms may be-exchanged for amino groups, .for instance in chlorinated polyisobutylenes, chlorinated: parafiin hydrocarbons with about 12-20,.ca13bon atoms,

A-.further-iclass 'of'compounds which may be employed;

according to-the present invention are-the polyimines, ire. compounds: whichcontain imino groups in their; chain .andwhich are .a'ccessiblein various ways, for in-' are obtainable by reaction of epichlorohydrin or butylene dioxide 'and similar alkylene oxideswithjammonia or primary or secondary aminesmay. aljsobe: employed as basic p'olymersaccordi g tofthis invention Furthermore basic, o y i cs mayf e entionedias suitablebinders. Theym'ay be obtained' -b y the reaction of -'dior p'olycarboxyl'rc acids containing. imino groups or their esters with diorj p olyamines,or of jdior poly: amines 'containing.imino groups with dior polycarboxylic'acid's or their esters. As an example of the {first named principleof reaction the,condensation product 'fromjminodipropifonic acid'and ethylene-diamine may be mentioned:

For the second named groupo'fjcompounds the reaction products of oxalic acid ester with diethylene' triaminelmay be takenas an example; CQCONH;(CH%)iN H )2NH:=

Similarlybasic. polyurethanesmaybe-employed according to the invention such as they are .forinstance obtained- Furthermore ,basic polyureas vmay beused as; basic polymers.. These polyureas are vobtainable..for.instance. dipr'imary aliphatic polyamine. contain;

pocess ot Reynolds (J. Am. Chem. Soc. 69/4,: page ing -NH groups in its molecule with a diisocyanate. As diprimary aliphatic polyamines, diethylene triamine, triethylene tetramine, dipropylene triamine, 'y,'y'-diamino dipropyl ether, diaminodipropyl tetramethylene diamine (Spermin), 'y,'y-diamino-propylmethylamine etc. may be employed. Tetramethylene diisocyanate, hexamethylene diisocyanate and other polymethylene diisocyanates are preferably used as diisocyanates in carrying out the reaction. a

Long chain compounds containing imino groups may also be obtained by linking high molecular polyamines. Thus, polybasic compounds such as are obtained by the addition of bifunctional amines to acrylonitrile and subsequent hydrogenation, may be linked to yield long chain compounds by reaction with diisocyanates, dicarboxylic acids, dichlorides, diacrylamides etc. For instance hexamethylene diamine is added to acrylonitrile on both sides and hydrogenated. The addition of the reaction product to a further acrylonitrile molecule and subsequent hydrogenation is repeated several times until the desired product is obtained:

which for instance may be prolonged by further reaction with one of the following bifunctional compounds:

Furthermore the following compounds may be employed as basic binders: basic polysaccharides, for instance ,so-called amine cellulose, additionproducts of ethylene imine and cellulose, hydrolysates of protein substances, for instance hydrolysates from glue, casein or gelatine, and aminolysates with polyamines.

Further monomeric polyamines which are suitable as binders are the hydrogenation products of compounds obtained by the reaction of-the hydrogenation product of the compound obtained by the reaction of pentaerythrite and four mols of acrylonitrile, acrolein and ammonia or amines, the reaction product of the acetal of chloroacetaldehyde and ammonia, the reaction products of glycerol-tri-sulfuric-acid-ester and ammonia, the polyamines obtained by the reaction of dior triallylamine with ammonia in the presence of sodium etc.

The binders may be used as free bases in aqueous or substantially aqueous solution. Preferably, however, the aqueous solutions of their salts are employed in order not to impair the stability of the treating solutions (printing pastes, slopping pastes, impregnating solutions etc.) by premature reaction of the bases with the polyfunc tional compounds. The salts of volatile acids are especially suitable as the volatile acids evaporate during the drying of the impregnated textiles and cross-linking starts immediately. Non-volatile acids may be employed if the basic groups are set free by an alkaline after-treatment, especially in those cases, where an alkaline aftertreatment is necessary in the course of the printing or dyeing process. As polyfunctional cross-linking agents compounds may be employed which contain two or more radicals capable of reaction with primary or secondary amino groups. Suitable compounds are for instance the so-called polyisocyanate-formers. By polyisocyanate-formers compounds are understood, which react like polyfunctional isocyanates atelevated temperatures (cf. French Patent' 876,285). As examples may be named addition products of one mol of a diisocyanate and two mols of a 1.3-diketone or 1.3-ketone ester like acetic acid ester or maleic acid ester. Especially well suited .are the addition products of bisulfites and polyfunctional isocyanates which possess the advantage of being water soluble.

Further cross-linking agents are those compounds containing at least two carboxylic acid groups (or salts thereof, for instance, ammonium salts), carboxylic acid halide groups, carbonamide groups, carboxyalkyl or carboxyaryl groups, hydroxymethyl groups, alkoxy methyl groups or a combination of these groups.

Examples ofthese compounds are: oxalic acid (or their salts), succinic acid, adipic acid, sebacic acid, adipic acid dichloride, cyanuric chloride, oxalamide, succinimide, dimethyl oxalate, diethyl malonate, diethyl adipate, methane tricarboxylic acid diphenylester, N cyanoimino-dicarboxylic-acid-diphenylester, the condensation product ofphenoxy-acetic acid with formaldehyde, hexamethylol melamineor its ethers, the soluble reaction product of dicyandiarnide with formaldehyde (German Patent 671,704). In addition, polymeric products containing a plurality of the above substituents may be used, for instance: polyacrylates, polyacrylamides, polymethylolrpolyacrylamides, acid polyesters from three mols of maleic acid anhydride and one mol of glycerol.

As cross-linking agents-there may also be employed compounds containing at least two epoxy groups or ethylene imine groups, for instance:

The reaction product of one mol cyanuric chloride with three mols of ethylene imine having the following formula:

CH2 CH2 I N I 0 fl v The reaction product of hexahydro-l,3,5-tricrylyl-striazine and two or three mols of ethylene imine, reaction products of phosphoric acid-alkylester-dichlorides and ethylene imine, reaction products of disulfochlorides and ethylene imine, for instance of m-phenylenedisulfochloride and two mols of ethylene imine. Furthermore, bis-epoxypropyl ether, butylene dioxide, the reaction product or" novolacs with epichlorohydrin, quaternary compounds from glycerol-chloroacetic acid ester and three mols of the addition product of epichlorohydrin and dimethylamine of the formula:

Furthermore compounds With'at least two olefinic double bonds may be used as cross-linking agents, for instance, hexahydro-1,3,S-triacrylyl-s-triaZine, allylstarch etc.

When volatile acids are employed we have found that the volatile acids are preferably used in an amount in excess of that necessary for dissolving the resinous polyarnines. Stability of the printing and padding pastes is improved thereby.

Our present invention is'further illustrated by the followingexamples-without being restricted thereto, theparts being by weight:

:Iheainvention is further illustrated :by the :following examples without being :restricted thereto, the parts being byweight.

Example 1 200 parts of the above 40% acetic acid-solution 200 parts of a-20% pigment dyestufi paste 1 6 parts of ,finely powdered hexahydro-1,3,5-triacrylyl-striazine 300*parts of tragacanth thickening 6521000 284 parts of Water is'pi'inte'd upon a cotton fabric. After printing it is'dried and the fabric is exposed to a'temperature of (SO-100 C. for 10-5 minutes. Besides a good feel, the printing design thus obtained exhibits excellent fastness properties.

Example 2 'A fixation of pigments according to the pad-dyeing process which is'fast'to washing is accomplished in the following manner:

"50 parts of'tragacanth thickening 65:1000 are stirred with 50 parts of the acetic acid solution of the basic ester as described in Example 1 and 10 parts of hexahydro- 1,3,S-triacrylyl-s-triazine into a level paste and diluted with-390 parts of cold water. About 10 parts of a 20% pigment dyestuff paste are stirred with 400 parts of water and added to the first solution through a fine hair sieve. A mixed fabric of cotton :and viscose rayon is passed through this padding liquor on a two-bowl padding machine, dried and heated as'described in Example 1. A dyeing is obtained with a good handle, excellent levelling and fastness. The resistance of the fabric to abrasion is improved by the pad-dyeing.

Example 3 The followingresist is printed on cotton fabriesz 300 parts of tragacanth 65: 1000 20.0 parts .Of the acetic acid solution of Example 1 200 parts of a 20% pigment dyestufi paste .16 parts of powdered haxahydro-l,3,S-triacrylyl-s-triazine 40- parts of anhydrous sodium acetate 50- parts of zinc oxide 170 parts of water It is then briefly dried and slop-paddedwith the'following mix:

, 30 parts of the dyestuffaccording to Schultzs dyestuff table, seventh edition, No. 1314 650 parts of water 50 parts of tragacanth 6511000 30 parts of ammonium thiocyanate 1:1 30 parts of sodium chlorate 1:2 10 parts of ammonium vanadate 1:100

Thereafter it is dried, steamed for 5 minutes, washed and soaped with soda at the boil. Fixation of the binding agent is carried out at' the same time as the developing and fixingof the dyestufl from the leuco-sulfuric acid ester on steaming. resist of excellent fastn'ess "is obtained.

According to thisrnethod, a colored v 8 .Exampla4 *A'plastic'col'ored resist under Variamine'Bluewvhich is'fastto Washing is obtained asfollows:

(a) 'Impregnatinga'fabric with 12 parts of o-oxyflnaphthoic acidanilide per 1000 parts of water onatwobowl paddingmachine, drying and (b) Printing with:

350 parts of tragacanth 65:1000

200 parts-of the 40% :acetic-acid solution of Example 1 200 parts of a 20% pigment dyestufi paste 16 parts of finely powdered hexahydro-l,3,5-triacryly1-striazine 100' parts of lactic. acid 100 .pa rts of water,

drying;

(c) "Developing with 20 parts'per'1000 parts o'f'water of the acid salt of the di'azo compound from 4-amino-4'- methoxydip'henylamine by running once'througha'padding machine, 'shortair passage, passing-the goodsthroug-h a hot bath which contains 10 parts of sodium 'bisulphite per 1000 parts of water. The fabricis then washed and suhsequentlysoaped with soda at the boil, washed and dried. Fixation of the pigment dyestuff is carried out partly -by drying and partly in analkaline soap bath.

Example 5 A cotton fabric is printed with a mix consisting of:

200 parts of tragacanth 65:1000 V 200 parts of the 40% acetic acid solution of 'Example 1 200-parts of a 20% pigment dyestuff paste 16 :parts :of finely powdered hexahydro-1,3,5-tritacrylyl-s-triazine parts-of anhydrous sodium acetate 1'50 parts :of. zinc :oxide 1 :1

174 parts of water,

thereafter dried and the printed fabric is padded on a foulard with a padding solution containing:

parts of aniline hydrochloride 40 parts of tragacanth 65 :100

5 parts of aniline dissolved in 220 parts of water 54 parts of potassium ferrocyanide dissolved in 220 parts of water 30 parts of sodium chlorate dissolved in 220 parts ;of water.

thereafter it i s'dried and subsequently steamed for 3minutes in a rapid ager and, at last, soapedwith'so'daat the boil. .There is obtained a colored resist under aniline black which is distinguished by brilliancy, sharp. outlines and excellent fixation of the pigment dyestufi.

. Example 6 An interpolymer containing parts :of styrene and ten parts of .acrylfluoride, dissolved in. pa1'ts of benzene 'is':added drop by drop to a solution of 30.:parts. of methylpropylenediamine:

in 100 parts of butanol. After the reaction is finished the solution is steam-distilled, the residue washed with wateryprecipitated from acetic acid solution with soda lye, washed and dried. The material thus obtained contains about two per cent basic nitrogen which can'be determined "by titration; It is soluble in'dilute'acetic acid'with Weak opalescence.

A printing paste containing:

250 parts of tragacanth thickening 65: 1000 400 parts of a 20 per cent weakly acetic acid solution of the basic polystyrene 200 parts of hexahydro-l,3,5-triacrylyl-s-triazine 130 parts of water is printed upon a cotton fabric. After printing, drying follows at 100 C. The printing design thus obtained exhibits excellent fastness properties.

Example 8 Example 9 160 parts of a polyester from adipic acid and ethyleneglycol with an hydroxyl number of 62 and an acid number of 0.6 is freed from Water at 130 C. in vacuo and 30 parts of hexanediisocyanate are added at 100 C. After stirring for an hour (the content of NCO is 3.96 per cent as calculated) the solution is diluted with 160 parts of chloroform and 17 parts of methylpropylenediamine in 100 parts of chloroform are added. Then the solvent is distilled oil and theresidue, containing about 1.5 per cent of basic nitrogen capable of being determined by .titration, is dissolved in a solution of water and the calculated quantity of acetic acid to yield a 40 per cent paste.

A printing paste, containing:

350 parts of tragacanth thickening 65 1000 250 parts of a 40 per cent weakly acetic acid solution of the basic polyester 200 parts of a 20 per cent pigment dyestuff paste 20 parts of hexahydro-l,3,5-triacrylyl-s-triazine 230 parts of water is printed upon a cotton fabric. After printing it is dried at 120 C. The printing design thus obtained is resistant to'light and Washing and the material has a soft hand.

Example 70 parts of vinylsuccinimide (M. P. 42 C.) obtained by addition of succinimide to acetylene, are mixed with 0.5 percent of benzoylperoxide and polymerized at 100 C. with cooling. The Weakly yellow, brittle polymer is heated for 18 hours to 120 C. with 200 parts of hydrazinehydrate, then precipitated and washed with alcohol. The polybasic compound obtained is diluted with the calculated quantity of acetic acid to yield a ten per cent viscous solution.

A- printing'paste, containing:

200 parts of tragacanth thickening 65: 1000 300 parts of a ten per cent solution of the acetate of the above polyvinylamine 250 parts of a 20 per cent pigment dyestulf paste 60 parts of hexahydro-l,3,S-triacrylyl-s-triazine 190 parts of water is printed on a cotton fabric. After printing the material is heated for 15 minutes to 100 C. The'printing design thus obtained is fast to light and washing.

Example J1 A polyamine obtained by reaction of chlorinated polyisobutylene (with a content of 26 per cent G1) with ammonia under pressure, having a content of about two per cent of basic nitrogen, is dissolved in dilute acetic acid and twelve per cent of hexahydro-1,3,5-triacrylyl-striazine (calculated on the weight of the polyamine) added. The resultant paste is applied to a staple rayon fabric by slopping. After centrifuging off the solution it is dried at C. The fabric thus treated can be dyed With three per cent of Fast W001 Blue BL "(Schultz' Farbstofitabellen No. 974) in vivid blue,

Example 12 A cotton fabric is printed with a printing paste of the following composition: 50 parts of polyethyleneimine (50 per cent) are diluted with water to 200 parts. 200 parts of Indahthrenbrown 'BR (Schultz Farbstofitabellen No. 1227) (pigmentdyestuff paste20 per cent) are stirred into this solution and diluted with 400 parts of water. Then 7-5 parts of acetic acid (50per cent) and 65 parts of the reaction product of potassium bisulfite and hexanediisocyanate are added, or instead, 60 parts of formaldehyde (30 per cent). 7

.Afte'r printing the material is dried shortly and reacted for five minutes at C. A brown print of excellent general fastness properties is obtained.

Example 13.

.' 15 parts of polyethyleneimine are dissolved in 45 parts reacted for five minutes at 100 C., a dyeing of excellent,

uniformity and general fiastness properties is obtained.

Example 14 v A cotton fabric is printed with: 50 parts of polyethyleneimine (50 per cent), dissolved in150 parts of water,

50 parts of methyl cellulose, 200 parts of Hansayellow G (Schultz Farbstofitabellen No. 84) (20 per cent), 100 parts of water, 75 parts of acetic acid (50 percent), 60 parts of sodium acetate, dissolved in parts of water, parts of zinc' oxide 1:1, 65 parts of the reaction product of potassium bisulfite and hexanediisocyanate.

After printing the fiabric is dried shortly and heated for five minutes to 100 C. The material is then passed through a slopped liquor containing: 85 parts of anilinechlorohydrate, 40 parts of tragacanth 65 :1000, five parts of aniline oil, 220 parts of water, 54 parts of potassium ferrocyanide dissolved in 200 parts of Water, 30 parts of sodiumchlorate, dissolved in 320 parts of water.

After padding the material is dried, treated with steam- Example 15 A solution is prepared, containing per liter 50 grams of the acetic acid salt of the addition product of three mols of w.w' diaminodipropylenediaminobutane ('Spermin) product of acrylonitrile and formaldehyde (triacrylforma1), 58 parts of glyoxal (30 per cent) or 45 parts of hexa' hydro-1,3,S-triacrylyl-s-triazine (dissolved in a mixture of water and acetone). A glass fabric is impregnated with this solution, centrifuged, and heated for ten minutes to C. The fabric is then dyed in .an acetic acid solut-ion with one per cent of Wool Fast Blue BL (Schultz Farbstofltabellen 1931, vol. I, No. 974). A full-shade, reddish blue dyeing of excellent fastness to water is. obtained.

'111 Example 16 pastecontaining:

isnprintedionza cotton fabric. After printing it is :dried andrzlreated iforifiveminutes to 100" 4C. .Arprinting of exeellentggeneral properties is obtained.

Example 17 aA pl-astic, colored resist of Va-riamin-Blue ;resistant to washing is obtained as follows:

to) -=Grounding 'of .a fabric with 12 parts orhydroxyrfina phthoic acid-anilide. -per litenon a'doublenollerypadding machine and drying,

( b) Printing with:

350 parts of tragacanth thickening (6521000) 50' parts of polyethylene imine (:50xper cent) "dissolved in l1'50-parts of water 200 :parts .of theaddition compound 'of hexamethylene- 'Fdiisocyanate and potassium bisulfite 100-parts of lactic acid 1l0 parts of water anddrying.

"('c) Developing with 20 grams of :the hydrochloride. of the diazo compound of '4-amino 4-methyoxydiphenylamine per liter in one passage over a slop-padding machine,a short :passage through air, passing of the fabric through ahot bath, containing ten grams per liter of sodium bisulfite. After rinsing the fabric is soaped hot with soda, then rinsed again and dried. The fixation of theipigment dyestuii is caused partly by dryingand partly by'thealkalinesoap bath.

Example '18 :A :basic :polyurea with the viscosity :number 11 :230, which: is :obtained from ,:0.2 .mol ,of 'diethylene triamine, 0.8:mo1 of -'y .'y-.diaminopr.opyl .methylamine and 1.0 mol of hexane ;;di-isocyanate, vis employed :for ;pigment printinginihefollowingpaste:

300;:parts of 2a 10% p'olyurea, 2'0 parts :of hexahydro-l .3.triacrylyl=s1triazine,

1501mm .of "copper phthalocyanine pigmQ-ntibIue,

"530 'parts 'of'water I000 parts.

The printing de igns obtained therewithshow :a very uniform, blue coloration and are very-,fast toli ght; and washing-.on cottonfabri-c and .staple'rayon fabric.

acetic acid solution of the basic "Example -1 9 50 parts of a aqueoussolution of the acetate of the basic polyurea consisting of 0.05 mol of diethylene triam-ine, 0.95 mol .of-e zyfldiaminodipropyl vmethyl'amine and 1:00 ;mol of hexane .fdiisocyanate iLareidiluted'with 1a0:.p.arts of tylose (702.1000) :and. 200 vpartsgof -water.

Flhereto. .are added 5 parts of,.hexahydroaL3zSgtriacrylyl-s-triazine and 2-4 parts of "the pigmentprinting paste 05-20%) and :the mixture is made up with vwater to form .1000 parts. .Theresultant pasteis :applied to .a staple rayon fabric by slop padding.

7 After sloppadding the material. is .(:a).heate.d...at 11:0- 13'0 C. for 5 minutes or (Ii) intermediately dried .at about '50-.60" 'C., or .the excess Water is removed by suction'filtering and'fixation. is. effected with alkalies, for instance of sodium carbonate or sodium hydroxidesolution-of'3 8 "B. ('23' gramsperlitre) at 4'0'-'50C. within about 7 seconds.

12 Slop-padding and fixation may be carried out-continuously. The printing design obtained has asoft hand and very good fastness to rubbing.

Example 20 A printing paste of the following composition is .applied to a cotton fabric:

1000 parts.

Afterprinting the fabric is subjected to'the actionof steam or reacted at C. for 5 minutes. The printing designs thus obtained are of excellent uniformity and very fast to light and Washing.

Example 21 A- fabric of polyacrylonitrile is dyed in a padding solution containing 1000 parts.

After :padding the material is dried and fixation is efiected as described inExample 24. The dyeing thus obtained has a soft hand and shows a very goodstability to boiling sodium carbonate solution.

Example 22 192 parts (1 mol) of epichlorohydrinzare introduced within 30 minutes into the55 'C..hot solution of 4813 70 parts of the above solution, 6 parts of a'15 percent blue copper phthalocyanine pigment IdYeStUlf paste, 910 parts :ofwater and 14 parts of hexahydro-1.3.S-triacrylyl-s-triazine (or oxalamide, or hexamethylol melamine) 1000 parts.

13 Example 23 i The printing paste containing:

action product of polybutyl aacrylate and lamino-3-methyl'amino propane,

200 parts of a 15% 6 parts of 'adipic acid suspended 50 parts of water,

pigment dyestufli' paste,

300 parts of tragacanth thickening (6521000), and

244 parts of water 1000 parts is printed on a cotton fabric.

After printing the fabric is dried and kept at 100 C.

for 10 minutes.

The printing design thus obtained shows a good hand and good fastness properties.

In the above be replaced by its salts, volatile bases such as ammonia.

Example 24 A printing paste containing 250 parts of tragacanth 400 parts of a 20% weekly ace basic polystyrene,

200 parts of .a 15% pigment dye printing paste the free adipic acid can preferably those containing thickening 65 1000) tic acid solution of a stuif paste,

8 parts of adipic acid diamide and 142 parts of water 1000 parts is applied to a cotton fabric.

After printing the fabric is dried at 100 C. The

printing design thus obtained is very fast to light and washing.

Instead of the amide, the ester,

for instance dimethylester, may be employed in the above printing paste with equal success.

The basic polystyrene is obtained by reacting a copolymer of 90 parts of styrene and 10 parts of acrylic acid fluoride with l-amino-B-methylamino propane.

Example 25 A cotton fabric is printed with:

25 parts of polyethylene imine 300 parts of methylcellulose (65 :1

200 parts of a 15% pigment dyestufi paste,

175 parts of glacial acetic acid,

parts of hexamethylol melamine or its hexamethyl ether, 65 parts of water 1000 parts.

After printing the fabric is dried shortly and reacted at 100 C. for 10 minutes.

A printing design of very Example 26 The printing paste consisting of:

200 parts of the 40% acetic acid polyacrylic ester according solution of the basic to Example 1,

200 parts of a pigment dyestuff paste,

10 parts of epichlorohydrin in 300 parts of methylcellulose (70: 1000) and 290 parts of water 1000 parts is applied to a cotton fabric. After drying the fabric is heated to 120 C. for 10 minutes. good fastness properties is obtained.

A printing design with 14 "Instead of epichlorohydrin, butylene dioxide maybe employed in the above printing paste with equal success.

, Example 27 15 parts of polyethylene imine (50%) are dissolved in are added. Cotton fabric is dyed with this padding mixture on the padding machine, subsequently dried and reacted at C. for 5 minutes. A dyeing of good uniformity and good fastness properties is obtained.

We claim:

1. A textile printing paste comprising a pigment, a thickening agent, an aqueous solution of a salt formed from an acid and a resinous aliphatic polyurea having recurring basic radicals selected from the group consisting of primary and secondary amino groups, and a polyfunctional compound selected from the group consisting of isocyanate addition products capable of setting free a polyisocyanate upon heating and hexahydro-1,3,5-triacrylyl-s-triazine, said basic radicals being the only groups in said resinous polyurea capable of reacting with the polyfunctional compound.

2. A textile printing paste comprising a pigment, a thickening agent, an aqueous solution of a salt formed from a volatile acid and a resinous aliphatic polyurea having recurring basic radicals selected from the group consisting of primary and secondary amino groups, and a polyfunctional compound selected from the group consisting of isocyanate addition products capable of setting free a polyisocyanate upon heating and hexahydro-l,3,5- triacrylyl-s-triazine, said basic radicals being the only groups in said resinous polyurea capable of reacting with the polyfunctional compound.

3. A textile printing paste as claimed in claim 2 wherein the polyfunctional compound is hexahydro-1,3,5-triacryIyl-s-triazine.

4. A textile printing paste comprising a pigment, a thickening agent, an aqueous solution of the acetic acid salt of the resinous basic polyurea from hexamethylenc diisocyanate and diethylenetriamine, and hexahydro-1,3,5- tn'acrylyl-s-triazine.

5. A thickening agent,

diisocyanate and 'y,'y'-diamino propyl methylamine, and hexahydro-l,3,5-triacrylyl-s-triazine.

6. The process of decorating textiles, which comprises applying to said textiles a printing paste as claimed in claim 1, and then rinsing said textiles in an aqueous solution of alkali to remove the acid constituent from the polymer salt contained in said paste.

7. The process of decorating textiles which comprises applying to said textiles a printing paste as claimed in claim 2, and then heating said textiles to remove the volatile acid from the polymer salt contained in said paste.

8. The process of decorating textiles which comprises applying to said textiles a printing paste as claimed in claim 3, and then heating said textiles to remove the basic polyurea from hexamethyleneclaim 5, and volatile acid paste.

then heating said textiles to remove the from the polymer salt contained in said 1 References Cited in the file of this patent UNITED STATES PATENTS Kleine'r et a1.

June 30, 1953 and... 

1. A TEXTILE PRINTING PASTE COMPRISING A PIGMENT, A THICKENING AGENT, AN AQUEOUS SOLUTION OF A SALT FORMED FROM AN ACID AND A RESINOUS ALIPHATIC POLYUREA HAVING RECURRING BASIC RADICALS SELECTED FROM THE GROUP CONSISTING OF PRIMARY AND SECONDARY AMINO GROUPS, AND A POLYFUNCTIONAL COMPOUND SELECTED FROM THE GROUP CONSISTING OF ISOCYANATE ADDITION PRODUCTS CAPABLE OF SETTING FREE A POLYISOCYANATE UPON HEATING AND HEXAHYDRO-1,3,5-TRIACRYLYL-S-TRIAZINE, SAID BASIC RADICALS BEING THE ONLY GROUPS IN SAID RESINOUS POLYUREA CAPABLE OF REACTING WITH THE POLYFUNCTIONAL COMPOUND. 